JPS58157808A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To prepare the titled polymer having high stereoregularity, in high yield, by treating a specific carrier with titanium tetrahalide and an aromatic carboxylic acid ester, compounding the resultant solid with an organo-Al compound and a pyridinecarboxylic acid ester, and using the composition as a catalyst. CONSTITUTION:A>=3C alpha-olefin is polymerized in the presence of a catalyst derived from (A) a solid obtained by reacting an aluminum halide with a silicon compound of formula (R<1> is 1-8C alkyl or phenyl; R<2> is 1-8C alkyl; m is 0, 1, 2 or 3), reacting the reaction product with the Grignard reagent of formula R<3> MgX (R<3> is 1-8C alkyl; X is halogen), treating the resultant carrier first with a titanium tetrahalide and then with an aromatic carboxylic acid ester, and contacting the product with titanium tetrahalide, (B) an organo-aluminum compound of formula AlR<4>3 (R<4> is 1-6C alkyl) and (C) a pyridinecarboxylic acid ester of formula II (R<5> is 1-12C alkyl; n is 1, 2 or 3).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for polymerizing alpha-olefins in the presence of novel catalysts.

In the presence of a solid catalyst component in which titanium is supported on a magnesium compound, an organoaluminium compound, and an aromatic carboxylic acid ester, such as a benzoic acid ester, a toluic acid ester, an anisic acid ester, a catalyst having a carbon number of 3 or more is prepared. -Many proposals have been made regarding methods for polymerizing olefins, such as propylene, to obtain highly stereoregular poly-α-olefins in high yields.

In almost all proposed methods, the generated poly
For the purpose of increasing the stereoregularity of α-olefins, the above-mentioned aromatic carboxylic acid esters are used together with solid catalyst components and organoaluminum compounds.

The present invention provides that a catalyst obtained by using a pyridine carboxylic acid ester together with a specific solid catalyst component and an organoaluminum compound has an α-olefin polymerization activity equivalent to that of a catalyst obtained using the above-mentioned aromatic carboxylic acid ester. It was completed based on the knowledge of showing.

In other words, the present invention is as follows.

(1) Aluminum halide and formula R temperature st(oR2)4-m
(:I) (In the formula, + R' represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, R2 represents an alkyl group having 1 to 8 carbon atoms, and is + m1do+ 11 2 or 3)
(2) The reaction product is expressed by the formula R3yt, yx
[ID (wherein R3 represents an alkyl group having 1 to 8 carbon atoms.

X represents a halogen atom).

(3)a) The obtained carrier is 4. Titanium rogenide.

or b) treating the support with titanium tetrahalide and an aromatic carboxylic ester.

(4) A solid catalyst component (A) obtained by contacting the treated solid with titanium chloride.

An organoaluminum compound (B) represented by the formula AtR: [III) (wherein R4 represents an alkyl group having 1 to 6 carbon atoms), and (wherein B5 represents an alkyl group having 1 to 12 carbon atoms).

Polymerization of α-olefin, characterized in that α-olefin having 3 or more carbon atoms is polymerized in the presence of a catalyst obtained from pyridine carboxylic acid ester (C) represented by (n is 1, 2 or 3) It's legal.

According to the present invention, poly-α-olefins with high stereoregularity can be obtained in high yields, so it is possible to omit the operation of removing catalyst residues from the poly-α-olefins produced.

The solid catalyst components used in the present invention include, for example.

Japanese Patent Application Laid-open No. 56-45909 filed by the present applicant,
Publication No. 56-163102, patent application No. 56-14036
It can be prepared according to the method described in No. 0 specification.

In the present invention, the solid catalyst component is prepared using substantially anhydrous compounds under an inert gas atmosphere such as nitrogen, arbo/etc.

Specific examples of aluminum halides in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, among which aluminum chloride is preferably used.

Specific examples of silicon compounds represented by formula [l] include:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-isopentoxysilane, tetra-n-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane.

Methyltri-n-butoxysilane, methyltriisopentoxysilane, methyltri-n-hexoxysilane, methyltriisooctoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopentoxysilane.

n-butyltriethoxysilane, isobutyltriethoxysilane, isopentyltriethoxysilane, isopentyltri-n-butoxysilane, dimethyljethoxysilane, dimethyldi-n-butoxysilane, dimethyldiisopentoxysilane.

Diethyljethoxysilane, diethyldiisopentoxysilane, di-n-butyljethoxysilane.

Diisobutyldiynepentoxysilane, trimethylmethoxysilane, trimethylethoxysilane.

Trimethylisobutoxysilane, triethylisopropoxysilane, tri-n-propylethoxysilane, tri-n-butylethoxysilane, triisopentylethoxysilane, phenyltriethoxysilane, phenyltriynebutoxysilane.

Examples include phenyltriisopentoxysilane, diphenyldiethoxysilane, diphenyldiimpe/toxysilane, diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and triphenylisopentoquinsilane.

What is the proportion of aluminum halide used in the reaction?

Per mole of silicon compound: 0.1 to 10 moles, especially 0
．． The amount is preferably 3 to 2 moles.

The reaction between aluminum halide and a silicon compound is usually carried out by combining both compounds in an inert organic solvent.

This is carried out by stirring for 0.1 to 2 hours at a temperature in the range of -50 to 100°C. The reaction proceeds exothermically and the reaction product is obtained as a solution in an inert organic solvent.

In addition, when using the tetraalkoxysilane whose circle is 0 in Formula 1 [I].

Small amounts of insoluble matter may be formed. This insoluble matter does not inhibit the polymerization activity of the final catalyst, but
In order to facilitate the preparation operation of the solid catalyst component, it is desirable to separate the solid catalyst components from the two reaction product mixtures. The reaction product is subjected to the reaction with the Grignard compound as a solution in an inert organic solvent.

Among the Grignard compounds represented by formula (Il), X
An alkylmagnesium chloride in which is a chlorine atom is preferably used, and specific examples thereof include.

Examples include methylmagnesium chloride, ethylmagnesium chloride, n-butylmagnesium chloride, and n-hexylmagnesium chloride.

The amount of Grignard compound used is 0.05 per mole of aluminum halide used for the preparation of the 2 reaction products.
~4 moles, particularly 1 to 3 moles is preferred.

There are no particular restrictions on the method of reacting the reaction product with the Grignard compound, but one step is to gradually add an ether solution of the Grignard compound or a mixed solvent solution of ether and an aromatic hydrocarbon to a solution of the reaction product in an inert organic solvent. Conveniently this is done by addition or addition in the reverse order. As for the ether above.

A compound represented by R'-0-R7 (in the formula, R6 and R7 represent an alkyl group having 2 to 8 carbon atoms) is preferably used, and specific examples thereof include diethyl ether diisopropyl ether, di-n -butyl ether, diisoamyl ether, etc.

The reaction temperature is usually -50 to 100°C, preferably -20 to
The temperature is 25°C. There is no particular restriction on the reaction time, but 1
Usually it is 5 minutes or more. As the reaction progresses, the carrier precipitates out. Although the carrier thus obtained can be subjected to the next treatment as a reaction product mixture, it is preferable to wash the produced carrier with an inert organic solvent before subjecting it to the treatment.

The carrier is then treated by the method (a) or (b) below.

(a) contacting the support with titanium tetrahalide in the presence or absence of an inert organic solvent at a temperature of 20 to 200°C, preferably 60 to 140°C, for 0.5 to 3 hours;
After this time, the support is separated from the reaction mixture, optionally washed with an inert organic solvent, and the titanium-contacted solid is then washed for 20-200 min in the presence or absence of an inert organic solvent.
A method of treating with an aromatic carboxylic acid ester at a temperature of 60 to 140°C, preferably for 0.5 to 3 hours.

(b) The m-isomer is treated with titanium tetrahalide and an aromatic carboxylic acid ester at 20 to 200°C, preferably at 60 to 140°C, in the presence or absence of an inert organic solvent.
A method of processing at a temperature of 0.5 to 3 hours.

Specific examples of titanium tetrahalide include titanium tetrachloride,
Examples include titanium tetrabromide and titanium tetraiodide.

Among them, titanium tetrachloride is preferably used. The amount of titanium chloride used is 1 mol or more per 1 mol of the Grignard compound used in preparing the carrier.

In particular, it is preferably 2 to 100 moles.

As an aromatic carboxylic acid ester.

[In the formula, R8 represents an alkyl group having 1 to 6 carbon atoms, Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -OR'(
R' represents an alkyl group having 1 to 4 carbon atoms] is preferably used.

Specific examples include methyl benzoate, ethyl benzoate, methyl toluate, and ethyl toluate.

Examples include methyl anisate and ethyl anisate. The amount of aromatic carboxylic acid ester to be used is 5 to 50% relative to the carrier.
Preferably it is 30% by weight, especially 15-25% by weight.

The treated solid thus obtained is separated from the treatment mixture and optionally washed with an inert organic solvent.

The treated solids are then contacted again with titanium chloride.

4. The amount of titanium halogenide used, the contact temperature and the contact time are the same as those in preparing the treated solid.

Therefore, it is separated and washed with an inert organic solvent. The titanium content of the solid catalyst component (A) is 0.5 to 5% by weight.

In the present invention, solid catalyst component (A) 2 formula CI[I]
An α-olefin having 6 or more carbon atoms is polymerized in the presence of a catalyst.

Specific examples of the organoaluminum compound (B) include:

Examples include triethylaluminum, triisobutylaluminum, and 1j-n-hexylaluminum, among which triethylaluminum and triimbutylaluminum are preferably used.

The amount of the organoaluminum compound (B) used is usually 1 to 100 per gram atom of titanium in the solid catalyst component (A).
It is 0 mole.

Specific examples of pyridine carboxylic acid ester (0) include:
2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4
-Pyridinecarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid.

2.5-pyridinedicarboxylic acid, 2.6-pyridinedicarboxylic acid, 3.4-pyridinedicarboxylic acid, 3.5-pyridinedicarboxylic acid, 2,3.4--pyridinetricarboxylic acid, 2,4.5-pyridine Tricarboxylic acid.

2.4.6-pyridinetricarboxylic acid, 3.4.5
- Alkyl esters of pyridinecarboxylic acids, such as pyridinetricarboxylic acid, for example methyl, ethyl.

Mention may be made of alkyl esters such as butyl, hexyl, octyl, tecyl, dodecyl. The amount of pyridine carboxylic acid ester (0) used is 0.05 to 0 per mole of organoaluminum compound (B) used for preparing the catalyst.
．． Preferably it is 6 mol.

Specific examples of the α-olefin having 6 or more carbon atoms to be polymerized by the method of the present invention include propylene, 1-phthene, 4-methyl-1-pentene, 1-hexene, and the like.

Furthermore, in the present invention, a mixture of α-olefins having 3 or more carbon atoms or the above α-olefin and ethylene may be copolymerized.

In the present invention, the double polymerization reaction can be carried out in the same manner as the polymerization reaction of α-olefins using a conventional Ziegler-Natsuta type catalyst.

The polymerization reaction can be carried out in liquid phase or gas phase.

When the polymerization reaction is carried out in a liquid phase, an inert organic solvent may be used as a polymerization medium, or the liquid α-olefin itself may be used as a polymerization solvent. There are no particular restrictions on the catalyst concentration in the polymerization solvent, but in general it is 1 polymerization solvent 1, and the solid catalyst component (A) is 0.00 in terms of titanium metal.
1 to 1 milligram atom, and 0.01 to 100 mmol for the organoaluminum compound (B).

In this invention, during the preparation of the solid catalyst component (A).

Examples of inert organic/organic solvents that may be used during the polymerization reaction include aliphatic hydrocarbons such as hexane and heptane, toluene, benzene, xylene natonoaromatic hydrocarbons, and halogenated products of these hydrocarbons. .

The polymerization reaction is carried out in the substantial absence of moisture and oxygen.

The polymerization temperature is usually 30 to 100°C, and the polymerization pressure is usually 1 to 80 Kf/cti1.

The molecular weight of the α-olefin polymer obtained by the method of the present invention can be easily adjusted by adding hydrogen to the monopolymerization system.

Next, examples will be shown. In the following description, "polymerization activity" refers to the polymer yield (g9) per hour of polymerization time per comb of solid catalyst component (A) IP used in the bipolymerization reaction, and "
H1■ means that the resulting polymer was heated with boiling n-hebutane for 20 minutes.
It is the weight percentage of the extraction residue based on the total polymer when time-extracted. In the Examples, all preparations of the solid catalyst component (A) were performed in a dry nitrogen gas atmosphere.

Example 1 (1) Preparation of solid catalyst component 15 mmol of anhydrous aluminum chloride was mixed with 40 tn of toluene.
Then, 15 mmol of methyltriethoxysilane was added, and the mixture was reacted at 25° C. for 0.5 hour with stirring, and then heated to 60° C. and further reacted for 1 hour. After the reaction product mixture was cooled to -5° C., 18 ml of diisoamyl ether containing 27 mmol of n-butylmagnesium chloride was added dropwise to the reaction product mixture over 0.5 hours while stirring. The temperature of the reaction system was maintained at -5°C. After finishing dropping,
The temperature was raised to 30°C and the reaction was delayed for 1 hour. The precipitated carriers were separated from each other and washed with toluene. Obtained carrier 4.9? After suspending the carrier in 25 mL of Otoluko and adding 150 mmol of titanium tetrachloride to this suspension, the temperature was raised to 90°C, and the support and titanium tetrachloride were brought into contact with each other for 1 hour while stirring. At the same temperature, the contact solid was separated and washed with n-hebutane and then toluene. Contact solid a, 1r with toluene 25m7! 6.5 mmol of ethyl benzoate was added to this suspension and kept at 90° C. for 1 hour with stirring. The treated solids were separated at 90°C and washed with n-hebutane and then toluene. Treated solids with toluene at 25mA! Suspend in

150 mmol of titanium tetrachloride was added to this suspension, and the treated solid was brought into contact with the titanium tetrachloride at 90° C. for 1 hour while stirring. The obtained solid catalyst component was separated from house to house at the same temperature, and
- Washed with hebutane. 6.52 ml of the solid catalyst component thus obtained was suspended in 80 m/n-hebutane. The titanium content of the solid catalyst component was 2.62% by weight.

(2) Into a separable flask with a propylene polymerization internal volume of 500 d, 0.009 mmol of ethyl 2-pyridinecarboxylate and then 200 rnl of n-hebutane were charged at room temperature under a nitrogen atmosphere.
After blowing propylene into the system and saturating it sufficiently, triethylaluminum 0
, 1 WL of an n-hebutane solution containing 15 mmol. After leaving the mixture at 60° C. for 10 minutes, 27.7~ of the solid catalyst component previously charged in a glass ampoule was added to initiate polymerization. Propylene was supplied into the polymerization system at a flow rate of 1 t/min, and unreacted propylene was discharged from the system to conduct normal pressure flow solvent polymerization for 60 minutes. After the polymerization reaction is completed.

The polymer slurry was transferred into 1 volume of isopropyl alcohol, and the inside was stirred for 10 minutes. The slurry is then filtered and
A white powder polymer was obtained, and glass fragments in the polymer were removed. 26. The resulting polymer was dried under reduced pressure at 60°C for 20 hours.
1F polypropylene was obtained. Polymerization activity is 942. H,
1 was 94.0%.

Example 2 The amount of ethyl 2-pyridinecarboxylate used was 0.018 mm! Polymerization of propylene was carried out in the same manner as in Example 1 except that the amount was changed to J mol.

Polymerization activity is 760. H, engineering, was 96.2%.

Example 6 The amount of ethyl 2-pyridinecarboxylate used was 0.027
Polymerization of propylene was carried out in the same manner as in Example 1 except that the amount was changed to mil/J mol.

Polymerization activity is 580. H, ■, was 97.5%.

Example 4 Propylene was polymerized in the same manner as in Example 3, except that 0.027 mmol of methyl 2-pyridinecarboxylate was used in place of ethyl 2-pyridinecarboxylate.

Polymerization activity is 630. H, ■, was 97.2%.

Example 5 Polymerization of propylene was carried out in the same manner as in Example 3 except that 0.027 mmol of butyl 2-pyridinecarboxylate was used in place of ethyl 2-pyridinecarboxylate.

Polymerization activity is 572. H, ■, was 97.5%.

Example 6 6.61 solid catalyst components were obtained in the same manner as in Example 1, except that 15 mmol of tetraethoxysilane was used in place of methyltriethoxysilane during the preparation of the solid catalyst components. The titanium content of the solid catalyst component was 2.84% by weight.

Polymerization of propylene was carried out in the same manner as in Example 1 using 25.6 cm of this solid catalyst component.

Polymerization activity is 890. H, ■, was 93.8%.

Example 7 The suspension of the solid catalyst component prepared in Example 1 was placed in a 2-ton autoclave equipped with a stirrer (as the solid catalyst component, 9
．． After a glass ampoule containing 0.5 m/l of n-hebutane solution containing 4M was attached to the autoclave, the air in the autoclave was replaced with nitrogen.

0.13 mmol of ethyl 2-pyridinecarboxylate.

Then, a solution of n-hebutane (15) containing 0.51 mmol of triethylaluminum was charged into the autoclave.

Then, 1200 m/l of liquid propylene was introduced into the autoclave and the autoclave was shaken. After heating the contents of the autoclave to 65°C, stirring was started, the glass ampoule was crushed, and propylene was polymerized at 65°C for 1 hour. After the polymerization reaction is completed, unreacted propylene is released, glass fragments are removed, and the resulting polypropylene is
It was dried under reduced pressure at ℃ for 20 hours. White powdered polypropylene 1382 was obtained. The polymerization activity was 94.5 at 14,700°H.

Example 8 Example except that 150 mmol of titanium tetrachloride and 6.5 mmol of ethyl benzoate were added to 25 mA' of a toluene suspension of 4.9 μl of the support and the support was treated by keeping at 90° C. for 1 hour. 1 was repeated. The titanium content of the solid catalyst component was 2.15% by weight. Polymerization activity is 935. ,H,
■ was 94.8%.

Example 9 Example 7 was repeated except that 10.2 cm of the solid catalyst component prepared in Example 8 was used. Polymerization activity is 14620, H
1 construction, was 95.3%.

Patent applicant: Ube Industries Co., Ltd.

Claims (4)

[Claims] (1) Aluminum halide and the formula R'mSi(OR2)4-m (in the formula, + R' represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, R2 represents an alkyl group having 1 to 8 carbon atoms, and 1 m is O', 1.2 or ro). (2) The reaction product is reacted with a Grignard compound represented by the formula R3MyX (wherein R3 represents an alkyl group having 1 to 8 carbon atoms and X represents a halogen atom). (3)a) The obtained carrier is titanium tetrahalide. or b) treating the support with titanium tetrahalide and an aromatic carboxylic acid ester. (4) A solid catalyst component (A) obtained by contacting the treated solid with titanium tetrahalide. An organoaluminum compound (B) represented by the formula AtR2 (wherein H4 represents an alkyl group having 1 to 6 carbon atoms), and (wherein + R5 represents an alkyl group having 1 to 12 carbon atoms; n is 1); .